JPH0543721B2 - - Google Patents
Info
- Publication number
- JPH0543721B2 JPH0543721B2 JP16620984A JP16620984A JPH0543721B2 JP H0543721 B2 JPH0543721 B2 JP H0543721B2 JP 16620984 A JP16620984 A JP 16620984A JP 16620984 A JP16620984 A JP 16620984A JP H0543721 B2 JPH0543721 B2 JP H0543721B2
- Authority
- JP
- Japan
- Prior art keywords
- starch
- etherification
- water
- sodium acetate
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920002472 Starch Polymers 0.000 claims description 28
- 239000008107 starch Substances 0.000 claims description 28
- 235000019698 starch Nutrition 0.000 claims description 28
- 238000006266 etherification reaction Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- VRYGRLBNIVQXMY-UHFFFAOYSA-M sodium;acetic acid;chloride Chemical compound [Na+].[Cl-].CC(O)=O VRYGRLBNIVQXMY-UHFFFAOYSA-M 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 239000001913 cellulose Substances 0.000 description 5
- 229920002678 cellulose Polymers 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920002230 Pectic acid Polymers 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229960001126 alginic acid Drugs 0.000 description 1
- 150000004781 alginic acids Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- LCLHHZYHLXDRQG-ZNKJPWOQSA-N pectic acid Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)O[C@H](C(O)=O)[C@@H]1OC1[C@H](O)[C@@H](O)[C@@H](OC2[C@@H]([C@@H](O)[C@@H](O)[C@H](O2)C(O)=O)O)[C@@H](C(O)=O)O1 LCLHHZYHLXDRQG-ZNKJPWOQSA-N 0.000 description 1
- 239000010318 polygalacturonic acid Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 150000004804 polysaccharides Chemical class 0.000 description 1
- 229920001592 potato starch Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
Description
本発明は高エーテル化度カルボキシメチル化澱
粉の製造法に関するものである。
カルボキシル基を有する多糖類には合成物で
は、カルボキシメチルセルローズ（CMC）、カル
ボキシメチル化澱粉（CMS）等が有り、繊維工
業、食品工業、医薬工業、紙・パルプ工業、濃薬
工業等で糊剤、増粘剤、粘結剤として使用されて
いる。しかし、天然物であるアルギン酸、ペクチ
ン酸は高価であること、価格の変動が大きく、ま
た高価であるため、さらにカルボキシル基を導入
することは、さらに不利である。
合成物の場合でも、天然のセルロース、澱粉を
使用しているものの、現在のところ供給が安定し
ていること、安価なモノクロール酢酸ソーダと反
応させることにより、見掛けの価格を下げること
が可能であること、また用途によりエーテル化度
を変化させることができる利点を有している。
但し、近年無計画な森林伐採が大きな社会問題
となつてきており、セルロースの安定供給も楽観
できない状況になりつつある。
そこで、澱粉に対する期待が高まりつつある
が、澱粉はセルロースに比較して、カルボキシメ
チル基が入り難く、エーテル化度はせいぜい0.7
〜0.8までで、これ以上の高エーテル化カルボキ
シメチル化澱粉の製造は極めて困難とする考え
が、常識となつている。従つて、カルボキシメチ
ル化澱粉の用途も、おのずと制限されたものにな
る。0.7〜0.8以上のエーテル化度のカルボキシメ
チル化澱粉の製造が極めて困難とする原因として
次のことが考えられる。
(1) 澱粉はセルロースと異なり、55℃以上の温水
で糊化し、取り扱い難く、また糊化温度以下で
あつても、アルカリによつて糊化することによ
り取り扱い難い。
(2) 上記(1)のごとく、澱粉はセルロースと異なる
性質を有するにもかからず、カルボキシメチル
セルロースと同じニーダー方式で検討されてい
た傾向にある。
(3) 水−溶剤系で反応する場合でも、澱粉が糊化
し易いため、溶剤の種類と澱粉に対する割合、
澱粉に対する水の割合等について、十分な検討
がされていなかつた。
本発明者は、これらの問題点を解消すべく、鋭
意研究の結果、高エーテル化カルボキシメチル化
澱粉の製造法を見い出し、本発明を完成したもの
である。即ち、
澱粉に対して0.8〜２重量倍の水および７〜15
重量倍のイソピルアルコールを加え、澱粉の糊化
温度以下で、苛性ソーダをモノクロール酢酸ソー
ダに対するモル比1.2以上、モノクロール酢酸ソ
ーダを澱粉に対するモル比（モノクロール酢酸ソ
ーダ／グルコース）2.0以上使用してマルセル化
およびエーテル化を行なうことを特徴とするエー
テル化度が1.0以上である高エーテル化度カルボ
キシメチル化澱粉の製造法を提供するものであ
る。
本発明では、澱粉に対して、0.8〜２重量倍の
水および、７〜15重量倍のイソピルアルコールを
使用するので、アルカリを添加しても澱粉が糊化
することなく、かつ適度に膨潤する。このことに
より、高エーテル化度カルボキシメチル化澱粉が
得られるものである。
次に本発明を実施例により具体的に説明する。
実施例
表−１に示す所定量のバレイシヨ澱粉、水およ
びイソプロピルアルコールを４ツ口セパラブルフ
ラスコに入れ攪拌する。30℃以下を保持しながら
タブレツト状の苛性ソーダを加え、１時間攪拌し
澱粉のマルセル化を行なう。次いで、30〜40℃の
温度範囲で所定量のモノクロール酢酸ソーダを添
加後、３時間攪拌し、酢酸を加え反応を終了す
る。反応物は25％含水メタノールで洗浄し、乾燥
することによりCMSの白色粉末を得る。
The present invention relates to a method for producing carboxymethylated starch with a high degree of etherification. Synthetic polysaccharides with carboxyl groups include carboxymethyl cellulose (CMC) and carboxymethylated starch (CMS), which are used as glue in the textile industry, food industry, pharmaceutical industry, paper/pulp industry, thick drug industry, etc. It is used as an agent, thickener, and binder. However, since alginic acid and pectic acid, which are natural products, are expensive, have large price fluctuations, and are expensive, it is even more disadvantageous to further introduce a carboxyl group. Even in the case of synthetic products, although natural cellulose and starch are used, the supply is currently stable, and the apparent price can be lowered by reacting with inexpensive monochlorosodium acetate. It also has the advantage of being able to change the degree of etherification depending on the application. However, in recent years, unplanned deforestation has become a major social problem, and the stable supply of cellulose is no longer optimistic. Therefore, expectations for starch are increasing, but compared to cellulose, it is difficult for starch to contain carboxymethyl groups, and the degree of etherification is only 0.7.
It is common knowledge that it is extremely difficult to produce highly etherified carboxymethylated starch with a value of up to 0.8. Therefore, the uses of carboxymethylated starch are naturally limited. The following may be considered to be the reason why it is extremely difficult to produce carboxymethylated starch having a degree of etherification of 0.7 to 0.8 or more. (1) Starch, unlike cellulose, gelatinizes with hot water above 55°C and is difficult to handle, and even at temperatures below the gelatinization temperature, it gelatinizes with alkali and is difficult to handle. (2) As mentioned in (1) above, even though starch has different properties from cellulose, it has tended to be studied using the same kneader method as carboxymethyl cellulose. (3) Even when reacting in a water-solvent system, starch tends to gelatinize, so the type of solvent and its ratio to starch,
Sufficient consideration was not given to the ratio of water to starch, etc. In order to solve these problems, as a result of intensive research, the present inventors discovered a method for producing highly etherified carboxymethylated starch, and completed the present invention. That is, 0.8 to 2 times the weight of water and 7 to 15 times the weight of starch.
Add twice the weight of isopyl alcohol, below the gelatinization temperature of starch, use caustic soda at a molar ratio of 1.2 or more to monochloro-sodium acetate, and use monochloro-sodium acetate to starch at a molar ratio of 2.0 or more (monochloro-sodium acetate/glucose). The present invention provides a method for producing carboxymethylated starch having a high degree of etherification, the degree of etherification being 1.0 or more, which is characterized by carrying out marcellization and etherification. In the present invention, water is used in an amount of 0.8 to 2 times the weight of starch, and isopyl alcohol is used in an amount of 7 to 15 times the weight of starch, so that even when alkali is added, the starch does not gelatinize and swells appropriately. do. By this, carboxymethylated starch with a high degree of etherification can be obtained. Next, the present invention will be specifically explained using examples. Example Predetermined amounts of potato starch shown in Table 1, water and isopropyl alcohol were placed in a 4-neck separable flask and stirred. While maintaining the temperature below 30°C, add tablet-shaped caustic soda and stir for 1 hour to marcelize the starch. Next, a predetermined amount of monochlorosodium acetate is added at a temperature of 30 to 40°C, followed by stirring for 3 hours, and acetic acid is added to complete the reaction. The reaction product is washed with 25% aqueous methanol and dried to obtain a white powder of CMS.
【表】
表−１の結果より、明らかなように澱粉に対す
る水およびイソプロピルアルコールの適当な使用
割合が有り、水の割合が少なくなるとエーテル化
度は上るものの、水および加温しても溶解しない
ミクロ状物の発生が見られた。また、水が多すぎ
ても、反応系がゲル状になり合成反応ができなか
つた。[Table] From the results in Table 1, it is clear that there is an appropriate ratio of water and isopropyl alcohol to starch, and as the ratio of water decreases, the degree of etherification increases, but it does not dissolve in water or even when heated. Occurrence of microscopic substances was observed. Moreover, even if there was too much water, the reaction system became gel-like and the synthesis reaction could not be carried out.
Claims (1)
15重量倍のイソピルアルコールを加え、澱粉の糊
化温度以下で、苛性ソーダをモノクロール酢酸ソ
ーダに対するモル比1.2以上、モノクロール酢酸
ソーダを澱粉に対するモル比（モノクロール酢酸
ソーダ／グルコース）2.0以上使用してマルセル
化およびエーテル化を行なうことを特徴とするエ
ーテル化度が1.0以上である高エーテル化度カル
ボキシメチル化澱粉の製造法。1 0.8 to 2 times the weight of water to starch and 7 to
Add 15 times the weight of isopyl alcohol, below the gelatinization temperature of starch, use caustic soda at a molar ratio of 1.2 or more to monochloro sodium acetate, and use a molar ratio of monochloro sodium acetate to starch (monochloro sodium acetate/glucose) of 2.0 or more. 1. A method for producing carboxymethylated starch with a high degree of etherification, which comprises carrying out marcellization and etherification.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16620984A JPS6143601A (en) | 1984-08-07 | 1984-08-07 | Preparation of carboxymethyl starch having high etherification degree |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16620984A JPS6143601A (en) | 1984-08-07 | 1984-08-07 | Preparation of carboxymethyl starch having high etherification degree |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6143601A JPS6143601A (en) | 1986-03-03 |
| JPH0543721B2 true JPH0543721B2 (en) | 1993-07-02 |
Family
ID=15827118
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16620984A Granted JPS6143601A (en) | 1984-08-07 | 1984-08-07 | Preparation of carboxymethyl starch having high etherification degree |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6143601A (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19622790A1 (en) * | 1996-06-06 | 1997-12-11 | Chem Fab Pirna Copitz Gmbh | Almost uncrosslinked carboxymethyl starch, process for its preparation, use of this modified starch as a retardant and a retarding pharmaceutical composition |
| CN1075516C (en) * | 1998-03-04 | 2001-11-28 | 中国科学院广州化学研究所 | Process for preparing high-viscosity and high-substitution value carboxymethyl amyloether |
| KR100468432B1 (en) * | 2002-09-04 | 2005-01-27 | 원영산업 주식회사 | Manufacturing method of textile printing polysaccharide |
| CN102153664B (en) * | 2011-01-17 | 2013-11-06 | 温州大学 | Method for preparing nanometer lamellar sodium carboxymethyl starch |
| CN102229675B (en) * | 2011-05-19 | 2012-11-28 | 湖北达雅化工技术发展有限公司 | Preparation method of food grade high viscosity sodium carboxymethyl starch |
| CN103509126A (en) * | 2012-06-21 | 2014-01-15 | 中国石油化工股份有限公司 | Preparation method for high-substitution degree carboxymethyl starch used for drilling fluid |
| CN106749712B (en) * | 2017-01-16 | 2019-04-09 | 无锡市善源生物科技有限公司 | A kind of method of semidry method preparation carboxymethyl starch |
-
1984
- 1984-08-07 JP JP16620984A patent/JPS6143601A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6143601A (en) | 1986-03-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4452978A (en) | Granular starch ethers having reduced pasting temperatures | |
| US2733238A (en) | Reaction of starch and alkylene oxides | |
| EP1969014B1 (en) | Process for starch modification | |
| US4663448A (en) | Aldehyde-containing heterpolysaccharides, a process for their preparation, and the use thereof | |
| US2148951A (en) | Organic starch derivatives and process | |
| CN101215334B (en) | Sago-based gelling starches | |
| CN101070351B (en) | Polysubstituted radical cellulose composite ether and its preparing method | |
| JPS59145201A (en) | Manufacture of highly substituted carboxyalkyl celluloses and mixed ethers | |
| US4112222A (en) | Method of preparing hydroxypropylated starch derivatives | |
| US4329181A (en) | Method for preparing alkaline corrugating adhesive | |
| Pal et al. | A comparative account of conditions of synthesis of hydroxypropyl derivative from corn and amaranth starch | |
| JPH0543721B2 (en) | ||
| US3751410A (en) | Starch derivatives | |
| US3236792A (en) | Water-dispersible form of dialdehyde polysaccharides and process therefor | |
| US3033852A (en) | Preparation of propionamide ethers of starch | |
| US2660577A (en) | Derivatization of starch witch lactones | |
| US5811541A (en) | Carboxymethyl-etherified starch derivatives and process for preparing the same | |
| US2451686A (en) | Starch compositions capable of forming water-soluble derivatives | |
| CN108164609B (en) | Carboxymethyl acetyl ether esterification synergistic composite modified starch and preparation method thereof | |
| US3135738A (en) | Modification of starch with n, n' methylene bisacrylamide, n-methylol acrylamide, or acrylamide and formaldehyde | |
| US4098997A (en) | Process for preparing cross-linked starches | |
| JP3572213B2 (en) | Low substituted hydroxypropylcellulose | |
| JPH0623355B2 (en) | Adhesive composition for corrugated board | |
| US3014901A (en) | Process for preparing ungelatinized starch ethers | |
| US2935509A (en) | Preparation of starch derivatives containing nitrogen |